Patent GB-723933-A (GB)
Title: Improvements in and relating to azo compounds
IPC: C09B29/033
Filed: 1952-06-23
Abstract: The invention comprises azo dyes of the formula <FORM:0723933/IV (c)/1> where R and R1 are C1-C10 alkyl, C3-C6 alkoxyalkyl or hydroxyalkoxyalkyl, C2-C5 hydroxyalkyl, C2-C4 sulphoalkyl, cyanoalkyl, sulphatoalkyl, phosphatoalkyl, phosphonoalkyl (the last four having 2-5 carbon atoms in the alkyl groups), b -nitroethyl, chlorallyl, C2-C4 alkenyl, or -(CH2)m-COOR2, m is 1-3, R2 is C1-C4 alkyl; X is hydrogen, C1-C6 alkyl, cyano, trifluoromethyl or phenyl (optionally substituted by nitro, chlorine, bromine, fluorine or C1-C4 alkyl); Z is C1-C4 alkyl, C1-C4 alkoxy or hydroxyalkoxy, chlorine, bromine, fluorine or -NH-CO-Y, Y is C1-C3 alkyl and n is 0-2.  These are made by diazotizing a 2-amino-4-X-5-nitrothiazole and coupling with the appropriate substituted aniline.  The dyes give dischargeable violet or blue shades on cellulose esters, polyamides, polyurethanes, polyethylene terephthalate, modified polyacrylonitrile, wool and silk.  Examples show the preparation of dyes from the following components, diazotization being effected with a solution of nitrosyl sulphuric acid in acetic and propionic acids; the coupling component is also dissolved in an acetic-propionic acid mixture, both solutions being substantially free from water.  Diazo components:-2-amino-5-nitrothiazole and its derivatives substituted in the 4-position by trifluoromethyl, cyano, m-nitrophenyl, methyl, n-butyl, phenyl and o-chlorophenyl.  Coupling components:-N : N-di-(b -hydroxyethyl) - m - toluidine, N : N - di - (b  - hydroxyethyl) - m - chloraniline, N - ethyl - N - (b  : g  - dihydroxypropyl) - m - toluidine, N - ethyl - N - (b  - methyl - b  : g  - dihydroxypropyl) - m - toluidine, N - (b  : g  - dihydroxypropyl) - N - (b  - methoxyethyl) - m - toluidine, N : N - di - (b -methoxyethyl) - m - toluidine, N - butyl - N - (b  - sulphatoethyl) - m - toluidine, N - (n - amyl)-N - (b  - sulphatopropyl) - m - ethylaniline, N - (b  - cyanoethyl) - N - (b  - phosphatoethyl) - m - chloraniline, N - methyl - N - (b  : g  - dihydroxypropyl) - m - toluidine, N : N - di - (b  - hydroxyethyl) - aniline, N - ethyl - N - (b  - sulphoethyl) - aniline, N - (n - butyl) - N - (b  - hydroxyethoxy - ethyl) - aniline, N - ethyl - N - (b  - hydroxyethyl) - m - toluidine, N - butyl - N - (b  : g  - dihydroxypropyl) - m - toluidine, N : N - di - (b  - hydroxyethyl) - 2 - methoxy - 5 - chloraniline, N - ethyl - N - (b  : g  - dihydroxypropyl)-aniline, N - ethyl - N - (b  - hydroxyethyl) - m - bromaniline, N - (b  - hydroxyethyl) - N - (b  - ethoxyethyl) - aniline, N - ethyl - N - (b  - hydroxyethyl) - aniline, N - ethyl - N - (4 : 5 - dihydroxyamyl) - aniline, N - (b  - hydroxyethyl) - N - (b  - cyanoethyl) - aniline, N - (b  - hydroxyethyl) - N - (b  - nitroethyl) - aniline, N - (b  - hydroxyethyl) - N - (b  - chlorallyl) - aniline, N - (b  - hydroxyethyl) - N - allylaniline, N - (b  - carbomethoxyethyl) - N - ethylaniline, N - (g  - carbomethoxypropyl) - N - (b  - hydroxyethyl) - m - toluidine, N : N - di - (b  - hydroxyethyl) - m - fluoraniline, N - (n - amyl) - N - (b  - hydroxyethyl) - aniline, N - ethyl - N - (b  - hydroxyethyl) - m - ethoxyaniline, N - (n - decyl) - N - (b  - hydroxyethyl) - aniline, N - (d  - sulphatobutyl) - N - ethylaniline, N - (d  - sulphobutyl) - N - ethylaniline, N - (b  - phosphonoethyl) - N - ethylaniline, N - (b  - phosphatoamyl) - N - ethylaniline, N : N - di - (b  - hydroxyethyl) - m - ethoxyaniline, N : N - di - (b  - hydroxyethyl) - m - acetaminoaniline, N - (b  - dimethylphosphatoethyl) - N - ethylaniline and N - (b  - dimethylphosphonoethyl)-N-ethylaniline.  Many other suitable components are mentioned.  The dyes may be applied to textile materials in aqueous dispersion together with sodium lignin sulphonate, turkey red oil, soap or oleyl glyceryl sulphate; the amount of dye can be 1/2 -3 per cent of the material.  The dyebath is heated to a temperature not above 70 DEG  C., the textile material then immersed and the temperature raised to 70-100 DEG  C. to complete dyeing.ALSO:2 - Amino - 4 - phenylthiazole and 2 - amino - 4 - (m - nitrophenyl) - thiazole are made by condensing acetophenone and m-nitro-acetophenone with thiourea and bromine.  2 - Amino - 4 - trifluoromethylthiazole is prepared from 1 : 1 : 1-trifluoro - 3 - chloro - 2 - propanone and thio - urea.  2 - Amino - 4 - cyanothiazole is similarly prepared from bromopyruvic nitrile and thiourea.  2 - Acetamino - 4 - phenylthiazole is obtained by acetylating the 2-amino compound.  5 - Nitro derivatives of the above are made by direct nitration.  2 - Amino - 4 - phenyl - 5 - nitrothiazole is obtained by hydrolysis of the 2-acetamino compound.ALSO:A solution of nitrosyl sulphuric acid is obtained by treating sodium nitrite with sulphuric acid and adding a mixture of propionic and acetic acids.